CN108554415A - A kind of cobalt zinc bimetallic catalyst and preparation method for Catalysts of Preparing Methyl Ethyl Carbonate - Google Patents
A kind of cobalt zinc bimetallic catalyst and preparation method for Catalysts of Preparing Methyl Ethyl Carbonate Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of cobalt zinc bimetallic catalyst and preparation method for Catalysts of Preparing Methyl Ethyl Carbonate, the cobalt zinc bimetallic catalyst (ZnCox/ NC T) it is using the Co/Zn ZIF synthesized under room temperature as presoma, under nitrogen atmosphere obtained by calcining.A series of bimetallic catalyst can be obtained by controlling cobalt zinc proportioning and calcination temperature.The catalyst is used for the ester exchange reaction Catalysts of Preparing Methyl Ethyl Carbonate of dimethyl carbonate and diethyl carbonate, and yield can reach 90% or more, and reaction condition is mild, and catalyst is easily isolated and recycled, and reusability is good.
Description
Technical field
The present invention relates to the preparation methods of cobalt zinc bimetallic catalyst, are specifically summarised as double based on ZIFs material preparation cobalts zinc
Metallic catalyst is catalyzed dimethyl carbonate and diethyl carbonate transesterification Catalysts of Preparing Methyl Ethyl Carbonate.
Background technology
It is developed so far as lithium battery gradually replaces lead-acid battery, the application of methyl ethyl carbonate (abbreviation EMC) receives extensively
General concern.As a kind of common excellent lithium battery solution, compared with traditional electrolyte solution, methyl ethyl carbonate can carry
The energy density and discharge capacity of high battery, the advantage in terms of security performance and service life also make it show fast development
The impetus.From a structural point, methyl ethyl carbonate is simplest asymmetric ester, contains methyl and ethyl in structure, has both
The property of dimethyl carbonate and diethyl carbonate is a kind of important organic synthesis intermediate.The commercially available universal valence of methyl ethyl carbonate
Lattice are higher to be synthesis and separating difficulty, and it is to push EMC hairs to prepare suitable catalyst to promote the production of high-purity methyl ethyl carbonate
The key of exhibition.
The synthetic method of common methyl ethyl carbonate includes phosgenation, oxidation carbonyl process and ester-interchange method, it is contemplated that production
Green and technique maturity, ester-interchange method is that report at present prepare the main method of dimethyl carbonate.Ester-interchange method
It can be divided into the transesterification (a) of methylchloroformate and ethyl alcohol, the ester of dimethyl carbonate and ethyl alcohol again according to the different of raw material are used
Exchange the transesterification (c) of (b) and dimethyl carbonate (DMC) and diethyl carbonate (DEC), the wherein reaction raw materials of route (a)
For toxic methylchloroformate, and by-product corrodes equipment, this method is gradually eliminated.Route (b) is industrially to use
A kind of relatively broad synthetic method, reaction condition is mild, and raw material green is harmless, but by-product first can be generated in reaction process
Alcohol, needing to remove methanol in time could promote reaction forward to move, and in addition to this, reactants and products can form 3 kinds of azeotropic bodies
System, it is more demanding to isolation technics.And route (c) not only has route (b) mild condition, the advantage of raw material green, and it is anti-
Midway no coupling product is answered to generate, it is even more important that reactants and products can be used as the electrolyte of lithium battery, reduce separation
Difficulty.
In recent years, the catalyst research of the ester exchange reaction of dimethyl carbonate and diethyl carbonate is concentrated mainly on heterogeneous
In catalysis, including solid base and novel metal organic frame (MOFs) material.(Zhen, L.S., the X.Z.Jiang such as Shen Zhenlu
And W.J.Zhao, A New Catalytic Transesterification for the Synthesis of Ethyl
Methyl Carbonate.Catalysis Letters, 2003.) find that the catalytic activity of MgO is best, target product yield can
To reach 44.2%, followed by ZnO.(Zhao, G., et al., Efficient the porous carbon- such as Jia Mingjun
supported MgO catalysts for the transesterification of dimethyl carbonate
With diethyl carbonate.Journal of Molecular Catalysis A Chemical, 2010.) pass through leaching
Stain method loads to MgO on NC-2 carriers, under suitable conditions the selectivity of MgO/NC-2 catalyzed transesterifications close to
The optimal yield of 100%, EMC are 49.3%.(Wang, J., et al., Magnesium the Aluminum Spinel such as Wang Jun
as an Acid-Base Catalyst for Transesterification of Diethyl Carbonate with
Dimethyl Carbonate.Catalysis Letters, 2014.) prepare one kind by evaporation-induced self-assembly has simultaneously
The magnesium aluminate spinels of solid acid and alkalinity, in the experiment of catalysis dimethyl carbonate and diethyl carbonate transesterification, this is urged
Agent shows excellent catalytic performance, and reaction 30min can reach balance.
MOFs is a kind of framework material that latest development is got up, because of its porosity, large specific surface area and thermal stability and change
Stability is learned to be also applicable in well in the ester exchange reaction of catalysis DEC and DMC.(Zhou, Y., the et al., Metal- such as ZhouY
organic frameworks as an acid catalyst for the synthesis of ethyl methyl
Carbonate via transesterification.Journal of Molecu1ar Catalysis A Chemical,
2009.) using MOF-5 materials as the ester exchange reaction of catalyst DEC and DMC, 50.1% EMC yields and several can be obtained
100% selectivity.(Zhou, X., et al., Zeolitic imidazolate the framework as such as ZhouX
efficient heterogeneous catalyst for the synthesis of ethyl methyl
Carbonate.Journal of Molecular Catalysis A Chemical, 2013.) by the way that method synthesis is stirred at room temperature
ZIF-8 materials, under the appropriate reaction conditions, the yield of target product EMC is up to 50.7%.Table is tested in the repetition of catalyst
Bright, which still can keep higher catalytic activity after using 3 times.
With the discovery and use of more and more new materials, the research of the catalyst in relation to being catalyzed DMC and DEC transesterifications
It is more and more diversified.Nevertheless, the yield of EMC is still relatively low, it is difficult to which large scale investment produces.Therefore, exploitation is efficient non-
Homogeneous catalyst is the key that research DMC and DEC ester exchange reactions.
Invention content
The present invention provides a kind of cobalt zinc bimetallic catalyst for Catalysts of Preparing Methyl Ethyl Carbonate, solves existing catalyst and urges
It is combined to the problem that EMC yields are low and Repeatability is poor, preparation process is simplified, optimizes reaction condition, improves carbonic acid first
The yield of ethyl ester.Present invention simultaneously provides a kind of preparation methods of the cobalt zinc bimetallic catalyst.
The cobalt zinc bimetallic catalyst ZnCo for Catalysts of Preparing Methyl Ethyl Carbonate of the present inventionx/ NC-T is under room temperature
The Co/Zn-ZIF of synthesis is presoma, under nitrogen atmosphere calcining gained, and wherein x is the ratio between the amount of cobalt zinc material, and T is calcining
Temperature, specific preparation flow are：
(1) according to cobalt zinc bimetallic catalyst ZnCoxThe ratio between the amount of cobalt zinc material in/NC-T x, by raw material cobalt salt and zinc
Salt is made into mixing salt solution, and 2-methylimidazole is added in aqueous slkali, and is mixed with mixing salt solution, and wherein x values are (0.5
~3): 1, the ratio of the sum of amount of cobalt zinc material is (1~5) in the amount and salt-mixture of 2-methylimidazole substance: 1, alkali soluble matter with it is mixed
The molar ratio for closing salt is (10~50): 1, a concentration of 13~18mol/L of aqueous slkali；
(2) said mixture is stirred at room temperature 0.5~6h, centrifuge after 3~8min with deionized water be cleaned multiple times to
Then pH is cleaned 3 times between 7~8 with methanol, product is dried 6~10h, centrifugal speed in 80 DEG C~120 DEG C baking ovens
8000~10000rmp obtains solid Co/Zn-ZIF；
(3) it is placed in tube furnace using solid Co/Zn-ZIF as presoma, 1~5h, wherein nitrogen is calcined under nitrogen atmosphere
Flow is 20~100ml/min, and calcination temperature T is 500~800 DEG C, and heating rate is 2~10 DEG C/min, obtains the double gold of cobalt zinc
Metal catalyst.
Further, in catalyst of the present invention, the cobalt salt in step (1) is cobalt nitrate, cobalt chloride or cobalt acetate, the zinc
Salt is zinc nitrate, zinc chloride or zinc acetate.
Further, in catalyst of the present invention, the solvent of mixing salt solution is deionized water or methanol in step (1).
Further, in catalyst of the present invention, the molar ratio of solvent and solute is in the mixing salt solution in step (1)
(100~200): 1.
Further, in catalyst of the present invention, the alkali in step (1) is sodium hydroxide solution or ammonium hydroxide.
Method of the preparation of the present invention for the cobalt zinc bimetallic catalyst of Catalysts of Preparing Methyl Ethyl Carbonate, includes the following steps：
(1) according to cobalt zinc bimetallic catalyst ZnCoxThe ratio between the amount of cobalt zinc material in/NC-T x, by raw material cobalt salt and zinc
Salt is made into mixing salt solution, and 2-methylimidazole is added in aqueous slkali, and is mixed with mixing salt solution, and wherein x values are (0.5
~3): 1, the ratio of the sum of amount of cobalt zinc material is (1~5) in the amount and salt-mixture of 2-methylimidazole substance: 1, alkali soluble matter with it is mixed
The molar ratio for closing salt is (10~50): 1, alkaline concentration is 13~18mol/L；
(2) said mixture is stirred at room temperature 0.5~6h, centrifuge after 3~8min with deionized water be cleaned multiple times to
Then pH is cleaned 3 times between 7~8 with methanol, product is dried 6~10h, centrifugal speed in 80 DEG C~120 DEG C baking ovens
8000~10000rmp obtains solid Co/Zn-ZIF；
(3) it is placed in tube furnace using solid Co/Zn-ZIF as presoma, 1~5h, wherein nitrogen is calcined under nitrogen atmosphere
Flow is 20~100ml/min, and calcination temperature T is 500~800 DEG C, and heating rate is 2~10 DEG C/min, obtains the double gold of cobalt zinc
Metal catalyst.
Further, in the method for the present invention, the cobalt salt in step (1) is cobalt nitrate, cobalt chloride or cobalt acetate, the zinc salt
Can be zinc nitrate, zinc chloride or zinc acetate.
Further, in the method for the present invention, the solvent in mixing salt solution in step (1) is deionized water or methanol.
Further, in the method for the present invention, the mole ratio of the solvent and solute in mixing salt solution in step (1) takes
It is worth ranging from (100~200): 1.
Further, in the method for the present invention, the alkali in step (1) is sodium hydroxide solution or ammonium hydroxide.
The present invention is prepared for a kind of cobalt zinc bimetallic catalyst, and cobalt zinc is two kinds of common transition metal, is used alone each
From metal oxide have certain catalytic effect to DMC and DEC ester exchange reactions, but EMC yields are not high.And cobalt zinc is double
Metallic catalyst have benefited from interaction between two kinds of metals and in preparation process new object phase that may be present generation,
Show more superior catalytic performance.Catalyst of the present invention is closed for the ester exchange reaction of dimethyl carbonate and diethyl carbonate
At methyl ethyl carbonate, yield can reach 90% or more, and reaction condition is mild, and catalyst is easily isolated and recycled, and reuse
Property is good.
Advantageous effect：Compared with prior art, the present invention haing the following advantages：
The existing heterogeneous base catalyst for Catalysts of Preparing Methyl Ethyl Carbonate mostly uses coprecipitation or prepared by infusion process
Monometallic or bimetallic oxide, specific surface area is small, and active site is single, and repeat performance is poor, methyl ethyl carbonate
Yield can not break through 50%.The present invention prepares cobalt zinc using Co/Zn-ZIF as presoma in the heating calcining of nitrogen atmosphere Program
Bimetallic catalyst has following advantages：Remain the regular morphology of ZIFs materials and orderly duct, large specific surface area, metal
And metal oxide particle grain size it is small, be uniformly dispersed, to greatest extent retain presoma in carbon and nitrogen make activity
Site is various, and the interaction between different metal improves catalytic activity and selectivity, and stability is high, and long lifespan easily recycles.
Specific implementation mode
Just the present invention will be further described for specific implementation case below, and the purpose of the present invention, feature and advantage will accordingly
More vivid display is obtained, but the present invention is not limited to following specific examples.
Embodiment 1：
The preparation of catalyst：0.5mmol cobalt nitrates, 1mmol zinc nitrates and 1.5mmol2- methylimidazoles are weighed respectively respectively
It is dissolved in 0.15mol deionized waters and 1.15ml (13mol/L) ammonium hydroxide, two solution mix rapidly, in room temperature item
0.5h crystallizations are continuously stirred under part, product is cleaned multiple times with deionized water until production by centrifugation (8000rmp, 3min)
The pH of product stablizes 7~8 or so, and then the dry 6h in 80 DEG C of baking ovens, gained ZIFs are put into the roasting of nitrogen tube furnace, with 2 DEG C/
Min is warming up to 500 DEG C, nitrogen flow 20ml/min, maintains 1h postcoolings to room temperature, obtains cobalt zinc bimetallic catalyst.
Embodiment 2：
The preparation of catalyst：Also known as 1mmol zinc chloride, 1mmol cobalt chlorides and 4mmol2- methylimidazoles is taken respectively to be dissolved in
In 0.3mol deionized waters and 2.86ml (14mol/L) ammonium hydroxide, two solution mix rapidly, at ambient temperature continuously
3h crystallizations are stirred, the pH stabilizations until product are cleaned multiple times by centrifugation (9000rmp, 4min), with deionized water in product
7~8 or so, then the dry 7h in 90 DEG C of baking ovens, gained ZIFs are put into the roasting of nitrogen tube furnace, are warming up to 6 DEG C/min
It 600 DEG C, nitrogen flow 50ml/min, maintains 3h postcoolings to room temperature, obtains cobalt zinc bimetallic catalyst.
Embodiment 3：
The preparation of catalyst：Also known as 3mmol zinc acetates, 1mmol cobalt acetates and 20mmol2- methylimidazoles is taken respectively to dissolve
In 0.8mol deionized waters and 13.33ml (15mol/L) ammonium hydroxide, two solution mix rapidly, at ambient temperature
6h crystallizations are continuously stirred, the pH until product is cleaned multiple times by centrifugation (10000rmp, 8min), with deionized water in product
Stablize 7~8 or so, then the dry 8h in 120 DEG C of baking ovens, gained ZIFs is put into the roasting of nitrogen tube furnace, with 10 DEG C/min
800 DEG C are warming up to, nitrogen flow is that 100ml/min maintains 5h postcoolings to room temperature, obtains cobalt zinc bimetallic catalyst.
Embodiment 4：
The preparation of catalyst：0.5mmol cobalt nitrates, 1mmol zinc nitrates and 1.5mmol2- methylimidazoles are weighed respectively respectively
It is dissolved in 0.15mol methanol and 1ml (15mol/L) ammonium hydroxide, two solution mix rapidly, at ambient temperature continuously
0.5h crystallizations are stirred, product is cleaned multiple times with deionized water until the pH of product is steady by centrifugation (8000rmp, 3min)
7~8 or so are scheduled on, then the dry 9h in 80 DEG C of baking ovens, gained ZIFs are put into the roasting of nitrogen tube furnace, are heated up with 2 DEG C/min
To 500 DEG C, nitrogen flow 20ml/min, maintains 1h postcoolings to room temperature, obtain cobalt zinc bimetallic catalyst.
Embodiment 5：
The preparation of catalyst：0.5mmol cobalt nitrates, 1mmol zinc nitrates and 1.5mmol2- methylimidazoles are weighed respectively respectively
It is dissolved in 0.15mol deionized waters and 0.94ml (16mol/L) sodium hydrate aqueous solution, two solution are blended in rapidly one
It rises, continuously stirs 0.5h crystallizations at ambient temperature, product is multiple with deionized water by centrifugation (8000rmp, 3min)
It cleans until the pH of product stablizes 7~8 or so, then dry 10h, gained ZIFs are put into nitrogen tube furnace in 80 DEG C of baking ovens
Roasting is warming up to 500 DEG C, nitrogen flow 20ml/min with 2 DEG C/min, maintains 1h postcoolings to room temperature, obtains the double gold of cobalt zinc
Metal catalyst.
Embodiment 6：
The preparation of catalyst：0.5mmol cobalt nitrates, 1mmol zinc nitrates and 1.5mmol2- methylimidazoles are weighed respectively respectively
It is dissolved in 0.15mol deionized waters and 0.83ml (18mol/L) sodium hydrate aqueous solution, two solution are blended in rapidly one
It rises, continuously stirs 0.5h crystallizations at ambient temperature, product is multiple with deionized water by centrifugation (8000rmp, 3min)
It cleans until the pH of product stablizes 7~8 or so, then dry 6h, gained ZIFs are put into nitrogen tube furnace in 80 DEG C of baking ovens
Roasting is warming up to 500 DEG C, nitrogen flow 20ml/min with 2 DEG C/min, maintains 1h postcoolings to room temperature, obtains the double gold of cobalt zinc
Metal catalyst.
Embodiment 7：
It weighs 0.1molDMC and 0.1molDEC to be placed in three-neck flasks of the 50ml with condensing unit, it is real that 1wt% is added
The catalyst of the preparation of example 1 is applied, mixture is heated to 100 DEG C, continuously stirs 3h at this temperature, and product is carried out using gas-chromatography
Quantitative analysis, product yield 91.1%, selectivity of product is close to 100%.
Embodiment 8：
It weighs 0.1molDMC and 0.1molDEC to be placed in three-neck flasks of the 50ml with condensing unit, it is real that 1wt% is added
The catalyst of the preparation of example 2 is applied, mixture is heated to 100 DEG C, continuously stirs 3h at this temperature, and product is carried out using gas-chromatography
Quantitative analysis, product yield 69.3%, selectivity of product is close to 100%.
Embodiment 9：
It weighs 0.1molDMC and 0.1molDEC to be placed in three-neck flasks of the 50ml with condensing unit, it is real that 1wt% is added
The catalyst of the preparation of example 3 is applied, mixture is heated to 100 DEG C, continuously stirs 3h at this temperature, and product is carried out using gas-chromatography
Quantitative analysis, product yield 79.3%, selectivity of product is close to 100%.
Embodiment 10：
It weighs 0.1molDMC and 0.1molDEC to be placed in three-neck flasks of the 50ml with condensing unit, it is real that 1wt% is added
The catalyst of the preparation of example 4 is applied, mixture is heated to 100 DEG C, continuously stirs 3h at this temperature, and product is carried out using gas-chromatography
Quantitative analysis, product yield 72.4%, selectivity of product is close to 100%.
Embodiment 11：
It weighs 0.1molDMC and 0.1molDEC to be placed in three-neck flasks of the 50ml with condensing unit, it is real that 1wt% is added
The catalyst of the preparation of example 5 is applied, mixture is heated to 100 DEG C, continuously stirs 3h at this temperature, and product is carried out using gas-chromatography
Quantitative analysis, product yield 76.7%, selectivity of product is close to 100%.
Embodiment 12：
It weighs 0.1molDMC and 0.1molDEC to be placed in three-neck flasks of the 50ml with condensing unit, it is real that 1wt% is added
The catalyst of the preparation of example 6 is applied, mixture is heated to 100 DEG C, continuously stirs 3h at this temperature, and product is carried out using gas-chromatography
Quantitative analysis, product yield 68.9%, selectivity of product is close to 100%.
Embodiment 13：
By used catalyst in embodiment 1, without any processing after being separated by filtration, it to be used for the cycle of next batch
Reaction, the reaction condition of circular response is identical as detection method as embodiment, after recycling 6 times, product yield 75.2%,
Selectivity of product is close to 100%.
According to the experimental result of case study on implementation 7-13, the present invention relates to a kind of cobalt zinc based on ZIFs material preparations it is double
Synthetic reaction of the metallic catalyst for methyl ethyl carbonate has efficient catalytic performance, can not only improve target product carbonic acid
The yield and selectivity of methyl ethyl ester, and there is excellent repeat performance, recycling 6 rear catalyst activity not
It occurs and is decreased obviously.In addition, the catalyst preparation process is simple, mild condition is not high to equipment requirement, is suitble to promote and send out
Exhibition.
Claims (10)
1. a kind of cobalt zinc bimetallic catalyst for Catalysts of Preparing Methyl Ethyl Carbonate, which is characterized in that catalyst Z nCox/ NC-T,
It is the Co/Zn-ZIF to synthesize under room temperature as presoma, calcining gained, wherein x are cobalt zinc material under nitrogen atmosphere
The ratio between amount, T is calcination temperature, and specific preparation flow is：
(1) according to cobalt zinc bimetallic catalyst ZnCoxThe ratio between the amount of cobalt zinc material in/NC-T x, raw material cobalt salt and zinc salt are matched
At mixing salt solution, 2-methylimidazole is added in aqueous slkali, and is mixed with mixing salt solution, wherein x values are (0.5~3):
1, the ratio of the sum of amount of cobalt zinc material is (1~5) in the amount and salt-mixture of 2-methylimidazole substance: 1, alkali soluble matter and salt-mixture
Molar ratio is (10~50): 1, a concentration of 13~18mol/L of aqueous slkali；
(2) 0.5~6h is stirred at room temperature in said mixture, is cleaned multiple times to pH 7 with deionized water after centrifuging 3~8min
Between~8, then cleaned 3 times with methanol, by product in 80 DEG C~120 DEG C baking ovens dry 6~10h, centrifugal speed 8000~
10000rmp obtains solid Co/Zn-ZIF；
(3) it is placed in tube furnace using solid Co/Zn-ZIF as presoma, 1~5h, wherein nitrogen flow is calcined under nitrogen atmosphere
It it is 500~800 DEG C for 20~100ml/min, calcination temperature T, heating rate is 2~10 DEG C/min, obtains cobalt zinc bimetallic and urges
Agent.
2. the cobalt zinc bimetallic catalyst according to claim 1 for Catalysts of Preparing Methyl Ethyl Carbonate, which is characterized in that described
Cobalt salt in step (1) is cobalt nitrate, cobalt chloride or cobalt acetate, and the zinc salt is zinc nitrate, zinc chloride or zinc acetate.
3. the cobalt zinc bimetallic catalyst according to claim 1 for Catalysts of Preparing Methyl Ethyl Carbonate, which is characterized in that described
The solvent of mixing salt solution is deionized water or methanol in step (1).
4. the cobalt zinc bimetallic catalyst according to claim 1,2 or 3 for Catalysts of Preparing Methyl Ethyl Carbonate, feature exists
In the molar ratio of solvent and solute is (100~200) in the mixing salt solution in the step (1): 1.
5. the cobalt zinc bimetallic catalyst according to claim 1,2 or 3 for Catalysts of Preparing Methyl Ethyl Carbonate, feature exists
In the alkali in the step (1) is sodium hydroxide solution or ammonium hydroxide.
6. a kind of method preparing the cobalt zinc bimetallic catalyst for Catalysts of Preparing Methyl Ethyl Carbonate, which is characterized in that this method packet
Include following steps：
(1) according to cobalt zinc bimetallic catalyst ZnCoxThe ratio between the amount of cobalt zinc material in/NC-T x, raw material cobalt salt and zinc salt are matched
At mixing salt solution, 2-methylimidazole is added in aqueous slkali, and is mixed with mixing salt solution, wherein x values are (0.5~3):
1, the ratio of the sum of amount of cobalt zinc material is (1~5) in the amount and salt-mixture of 2-methylimidazole substance: 1, alkali soluble matter and salt-mixture
Molar ratio is (10~50): 1, a concentration of 13~18mol/L of aqueous slkali；
(2) 0.5~6h is stirred at room temperature in said mixture, is cleaned multiple times to pH 7 with deionized water after centrifuging 3~8min
Between~8, then cleaned 3 times with methanol, by product in 80 DEG C~120 DEG C baking ovens dry 6~10h, centrifugal speed 8000~
10000rmp obtains solid Co/Zn-ZIF；
(3) it is placed in tube furnace using solid Co/Zn-ZIF as presoma, 1~5h, wherein nitrogen flow is calcined under nitrogen atmosphere
It it is 500~800 DEG C for 20~100ml/min, calcination temperature T, heating rate is 2~10 DEG C/min, obtains cobalt zinc bimetallic and urges
Agent.
7. the method according to claim 6 for preparing cobalt zinc bimetallic catalyst, which is characterized in that in the step (1)
Cobalt salt be cobalt nitrate, cobalt chloride or cobalt acetate, the zinc salt be zinc nitrate, zinc chloride or zinc acetate.
8. according to the method for preparing cobalt zinc bimetallic catalyst described in claim 6,7 or 8, which is characterized in that the step
(1) solvent of mixing salt solution is deionized water or methanol in.
9. according to the method for preparing cobalt zinc bimetallic catalyst described in claim 6,7 or 8, which is characterized in that the step
(1) molar ratio of solvent and solute is (100~200) in the mixing salt solution in: 1.
10. according to the method for preparing cobalt zinc bimetallic catalyst described in claim 6,7 or 8, which is characterized in that the step
(1) alkali in is sodium hydroxide solution or ammonium hydroxide.
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| CN113019453A (en) * | 2019-12-24 | 2021-06-25 | 中国科学院成都有机化学有限公司 | Catalyst for synthesizing diphenyl carbonate catalyst, preparation method and application |
| CN113371687A (en) * | 2021-06-18 | 2021-09-10 | 广东省武理工氢能产业技术研究院 | Porous heterostructure catalytic material and preparation method thereof |
| CN113797973A (en) * | 2021-08-26 | 2021-12-17 | 福州大学 | Method for rapidly preparing alkaline framework material catalyst and application |
| CN114149363A (en) * | 2021-10-20 | 2022-03-08 | 吉林师范大学 | Pyridine acrylate crystal, preparation method and application thereof in preparation of methyl ethyl carbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106694046A (en) * | 2016-12-21 | 2017-05-24 | 湘潭大学 | Preparation method of modified zeolite-like imidazole framework material, and application of material in carbon dioxide hydrogenation reaction |
-
2018
- 2018-05-29 CN CN201810537028.7A patent/CN108554415A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106694046A (en) * | 2016-12-21 | 2017-05-24 | 湘潭大学 | Preparation method of modified zeolite-like imidazole framework material, and application of material in carbon dioxide hydrogenation reaction |
Non-Patent Citations (1)
| Title |
|---|
| LINA CHONG ET AL.: "nvestigation of Oxygen Reduction Activity of Catalysts Derived from Coand Co/Zn Methyl-Imidazolate Frameworks in Proton Exchange Membrane Fuel Cells", 《CHEM ELECTRO CHEM》 * |
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| CN110813300B (en) * | 2019-12-02 | 2022-08-09 | 华北电力大学（保定） | Cobalt-zinc-loaded bimetallic nano-carbon material, preparation method thereof and application thereof in catalytic oxidation of magnesium sulfite |
| CN113019453A (en) * | 2019-12-24 | 2021-06-25 | 中国科学院成都有机化学有限公司 | Catalyst for synthesizing diphenyl carbonate catalyst, preparation method and application |
| CN113019453B (en) * | 2019-12-24 | 2022-12-16 | 中国科学院成都有机化学有限公司 | Catalyst for synthesizing diphenyl carbonate, preparation method and application |
| CN111250131A (en) * | 2020-01-16 | 2020-06-09 | 辽宁大学 | Co3ZnC/Co @ NGC magnetic wave-absorbing material and preparation method and application thereof |
| CN111250131B (en) * | 2020-01-16 | 2022-11-29 | 辽宁大学 | Co 3 ZnC/Co @ NGC magnetic wave-absorbing material and preparation method and application thereof |
| CN113371687A (en) * | 2021-06-18 | 2021-09-10 | 广东省武理工氢能产业技术研究院 | Porous heterostructure catalytic material and preparation method thereof |
| CN113371687B (en) * | 2021-06-18 | 2024-02-20 | 广东省武理工氢能产业技术研究院 | Porous heterostructure catalytic material and preparation method thereof |
| CN113797973A (en) * | 2021-08-26 | 2021-12-17 | 福州大学 | Method for rapidly preparing alkaline framework material catalyst and application |
| CN113797973B (en) * | 2021-08-26 | 2023-11-17 | 福州大学 | Method for rapidly preparing alkaline framework material catalyst and application thereof |
| CN114149363A (en) * | 2021-10-20 | 2022-03-08 | 吉林师范大学 | Pyridine acrylate crystal, preparation method and application thereof in preparation of methyl ethyl carbonate |
| CN114149363B (en) * | 2021-10-20 | 2023-08-22 | 吉林师范大学 | Pyridine acrylate crystal, preparation method and application thereof in preparation of ethyl methyl carbonate |
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